CN102690683B

CN102690683B - Catalytic cracking method and catalytic cracking device for producing propylene

Info

Publication number: CN102690683B
Application number: CN201110072785.XA
Authority: CN
Inventors: 高永灿; 谢朝钢; 张久顺; 朱金泉; 崔琰; 杨轶男; 马建国; 姜楠; 鲁维民
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2011-03-25
Filing date: 2011-03-25
Publication date: 2015-01-14
Anticipated expiration: 2031-03-25
Also published as: CN102690683A

Abstract

The invention discloses a catalytic cracking method and a catalytic cracking device for producing propylene. The catalytic cracking method comprises the following steps that one or more heavy raw materials and a first catalytic cracking catalyst containing Y-type zeolite and beta-type zeolite undergo a contact reaction in a first riser reactor; after the contact reaction, the first catalytic cracking catalyst is subjected to steam stripping and regeneration and then is recycled; one or more light hydrocarbons and a second catalytic cracking catalyst comprising shape-selective zeolite having aperture sizes less than 0.7nm undergo a contact reaction in a second reactor comprising a riser-fluidized bed tandem reactor; and after the contact reaction, the second catalytic cracking catalyst is subjected to steam stripping and regeneration and then is recycled. The catalytic cracking device adopts a double-reactor structure. A separator plate is arranged in a stripper of the catalytic cracking device and divides the stripper into two independent stripping zones, wherein one of the two independent stripping zones and one reactor form one reaction and stripping route; and the other one of the two independent stripping zones and the other reactor form the other one reaction and stripping route. The catalytic cracking method has high propylene and butene yields.

Description

A kind of catalyst cracking method and device producing propylene

Technical field

The present invention relates to a kind of catalyst cracking method and the device of producing propylene.

Background technology

Heavy oil catalytic pyrolysis is the important method preparing the small-numerator olefins such as ethene, propylene and butylene, the method of the heavy oil fluid catalytic cracking production low-carbon alkene of industrial use such as produces the deep catalytic cracking technology (DCC of propylene, USP4980053 and USP5670037) and produce the catalytic pyrolysis technology (CPP of ethene, USP6210562), these two kinds of methods adopt single riser reactor or single riser reactor combination dense phase fluidized bed structure of reactor to coordinate special-purpose catalyst to react under higher temperature conditions.The catalyzer used is the single catalyst system containing the mesopore zeolite with MFI structure (such as ZSM-5) and/or large pore zeolite (as Y zeolite) isoreactivity constituent element, and higher small-numerator olefin productive rate is pursued on the certain heavy oil conversion basis of guarantee.But, because strengthening heavy oil conversion differs greatly with the catalytic active center improved required for small-numerator olefin, therefore, its catalyst formulation is difficult to combine in the reactor of dense phase fluidized bed at single riser reactor or single riser reactor the requirement simultaneously taking into account heavy oil conversion reaction and the reaction of voluminous small-numerator olefin sometimes.In addition, some catalytic cracking unit also increases voluminous small-numerator olefin productive rate by the auxiliary agent method of adding containing ZSM-5 zeolite at present.Although the method has good handiness, but the method is except increase small-numerator olefin productive rate amplitude is less, also there is the defect that other is difficult to overcome: one is, when add containing ZSM-5 zeolite auxiliary agent very little time be difficult to reach voluminous small-numerator olefin requirement; Two are, when adding the auxiliary agent containing ZSM-5 zeolite and being higher, main catalytic cracking catalyst are existed again to the effect of significant adverse, reduce whole catalyst system net effect, also there is the problem that between auxiliary agent with Primary Catalysts, performance is mated mutually simultaneously.

CN100448954C discloses the catalysis conversion method of propylene enhancing.The method adopts two kinds of catalyst mixtures to participate in reaction, and a kind of is the catalyzer containing y-type zeolite, and another kind of is the catalyzer containing ZSM-5 zeolite, transition metal additives and phosphorus additive.Reaction unit adopts double lifting leg design, mainly comprises main riser tube, subsidiary riser and public revivifier and gas-solid separation equipment.At main riser tube, heavy, macromolecular hydrocarbon oil crude material cracking are generated the products such as gasoline, diesel oil and liquefied gas; Isolate the liquefied gas intermediate product after propylene to be injected in auxiliary riser line reactor and to contact with two kinds of catalyst mixtures of heat, successively carry out alkene oligomerization, superimposed product cracking and dehydrating alkanes and react propylene enhancing product.The method does not relate to the side effect solving and disturb between above-mentioned two kinds of catalyzer, and productivity of propylene is not high; Stripper and regenerator configuration is not related to yet.

CN101314724A discloses a kind of bio-oil and mineral oil combined catalytic conversion method.The method adopts catalyzer catalyzed conversion bio-oil and the mineral oil in riser tube and fluidized-bed compound reactor that modified beta zeolite and the zeolite with MFI structure are essential active to be used for producing the small-numerator olefins such as propylene.The method uses the single catalyst system containing various active constituent element, be difficult to take into account heavy oil conversion reaction and voluminous small-numerator olefin reacts the very large reaction of two species diversity simultaneously, the side effect disturbed between above-mentioned two kinds of zeolites cannot be solved, also do not relate to stripper and regenerator configuration.

In catalytic cracking process, the regeneration of spent agent is one of core process of FCC apparatus.In regenerative process, not only recover the activity and selectivity of catalyzer, also for cracking reaction process provides the heat needed for reaction.Therefore, the revivifier pattern of catalytic cracking unit, structure also also exists variation, such as, " refining of petroleum and chemical industry " the 32nd the article " two-stage regeneration of catalytic cracking and application at home " of volume the 4th phase to indicate in a kind of single device device two-stage regeneration form side by side, a dividing plate is adopted close for revivifier phase section to be divided into two independently regenerator bed be furnished with corresponding independent main air in this revivifier, revivifier dilute phase section is public, two strands of flue gases discharger after dilute phase section is converged, spent agent then sequentially passes through first, flow out after completing coke burning regeneration after second two-stage regeneration device and participate in follow-up circulating reaction, regenerative process.Therefore, above-mentioned regenerator configuration only solves the regeneration issues of single catalyst system too.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of catalyst cracking method producing propylene, and the method has higher productivity of propylene.

The invention provides a kind of catalytic cracking method producing propylene, comprising:

(1) heavy feed stock and the first catalytic cracking catalyst contact reacts in the first riser reactor being chief active constituent element with y-type zeolite and β zeolite is made, reacted oil gas is separated with the first catalytic cracking catalyst, oil gas introduces product separation system, first catalytic cracking catalyst introduces the first revivifier regeneration after the first stripper stripping, and regenerated catalyst is introduced the first riser reactor and recycled; First riser reactor temperature of reaction is 450 ~ 650 DEG C, and agent-oil ratio is 1 ~ 25, and the reaction times is 0.50 ~ 10 second;

(2) make light hydrocarbon and be less than 0.7nm with aperture and select the second catalytic cracking catalyst that shape zeolite is chief active constituent element in the second riser reactor contact reacts, reacted oil gas and reacted second catalytic cracking catalyst are introduced the fluidized-bed reactor of connecting with the second riser reactor and are reacted; The reacted oil gas of fluidized-bed reactor introduces product separation system, and reacted second catalytic cracking catalyst introduces Second reactivator regeneration after introducing the second stripper stripping; The second catalytic cracking catalyst after regeneration is introduced the second riser reactor and is recycled; Described light hydrocarbon comprises gasoline fraction and/or C4 hydrocarbon; When comprising gasoline fraction, the agent-oil ratio that gasoline fraction operates in the second riser reactor is 10 ~ 30, and the reaction times is 0.10 ~ 1.5 second; When described light hydrocarbon comprises C4 hydrocarbon, it is 12 ~ 40 that C4 hydrocarbon operates agent-oil ratio in the second riser tube, and the reaction times is 0.50 ~ 2.0 second; The temperature of reaction of fluidized-bed reactor is 500 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 35 hour ^-1.

The catalyst cracking method of production propylene provided by the invention, adopts different reaction environments, and highly selective transforms corresponding hydrocarbon oil cut, and while realizing improving heavy oil conversion rate, highly selective increases the yield of small-numerator olefin yield especially propylene.In heavy feed stock catalytic conversion reaction, reprocessing cycle system, adopt the catalytic cracking catalyst being chief active constituent element with Y type and β zeolite, in light hydrocarbon oil catalytic conversion reaction, reprocessing cycle system, employing is less than 0.7nm with mean pore size and selects the catalyzer of shape zeolite for chief active constituent element, fully, easily can strengthen heavy oil conversion, heavy feed stock and light hydrocarbon are converted into the small-numerator olefin products such as propylene by highly selective.Two reacted spent agents of reactive system enter respective breeding blanket, are easy to regulation and control, meet coke burning regeneration requirement, thus define two independences closed catalyst reaction, reprocessing cycle.Adopt different reaction environments to different raw materials, highly selective transforms corresponding hydrocarbon oil cut, and while realizing improving heavy oil conversion rate, highly selective increases the yield of small-numerator olefin yield especially propylene.

Accompanying drawing explanation

Fig. 1 is the schematic flow sheet of a kind of catalytic cracking unit provided by the invention and catalyst system thereof.Wherein 1,2 is riser reactor, 3 is dense fluidized bed bioreactor, 4 is revivifier, 5 is settling vessel and stripper subregion dividing plate, 6 regenerate subregion dividing plate in revivifier, 7 is heavy hydrocarbon oil riser reactor outlet gas-solid fast subset, and 8 be the fast subset of outlet gas-solid of riser tube and fluidized-bed combined reactor, and 9 is the public reacting-settler of riser reactor 1 and riser tube 2 and fluidized-bed 3 combined reactor.40 and 41 are respectively two strands of regenerated catalyst inclined tubes (by guiding valve aperture control catalyst flow wherein, do not mark in figure), 42 and 43 are respectively two strands of reclaimable catalyst inclined tubes (by guiding valve aperture control catalyst flow wherein, do not mark in figure), 51 and 52 are respectively stripping zone corresponding to two strands of catalyzer, 61 and 62 are respectively breeding blanket corresponding to two strands of catalyzer, and 50 is stripping steam introduction pipe line, and 60 is regeneration air introduction pipe line.As shown in Figure 1, riser reactor 2 is connected with fluidized-bed reactor 3 and is realized being arranged in parallel by settling vessel 9 and riser reactor 1, settling vessel 9 with comprise the stripper of stripping zone 51 with stripping zone 52 and be connected.

Embodiment

The catalyst cracking method of production propylene provided by the invention, in the first riser reactor, heavy feed stock and catalyst exposure are reacted the oil agent mixture generated and are separated with carbon deposited catalyst after reaction by oil gas by riser tube end tripping device, and oil gas is separated through follow-up product separation system and obtains the products such as cracked gas, pyrolysis gasoline, cracking light oil and cracking masout; Spent agent (carbon deposited catalyst) enters the first follow-up stripper, and the spent agent after stripping returns the first riser reactor after importing the first revivifier regeneration by line of pipes and recycles.Described tripping device is preferably fast separating device, in order to by reaction oil gas and carbon deposited catalyst sharp separation, can adopt existing fast separating device, and preferred fast packing is set to slightly revolves a point separator.By heavy hydrocarbon oil catalyzed conversion riser reactor end fast separating device, oil gas is separated rapidly with carbon deposited catalyst after reaction, dry gas yied can be reduced, suppress low-carbon alkene especially propylene transforming again after generating; The spent agent that separation obtains enters the first stripper and the first revivifier carries out stripping and regeneration, and process is easy to regulation and control, and can reach coke burning regeneration requirement.Operational condition in first riser reactor comprises: temperature of reaction is 450 ~ 650 DEG C, is preferably 480 ~ 600 DEG C; Agent-oil ratio is 1 ~ 25, is preferably 5 ~ 20; Reaction times is 0.50 ~ 10 second, is preferably 1 ~ 10; Reaction pressure (absolute pressure) 0.1 ~ 0.4MPa, is preferably 0.15 ~ 0.35MPa.

In the catalyst cracking method of production propylene provided by the invention, described heavy feed stock is heavy hydrocarbon and/or the various animals and plants oils raw materials being rich in hydrocarbon polymer, and described heavy hydrocarbon is selected from one or more the mixture in petroleum hydrocarbon, mineral oil and synthetic oil.Petroleum hydrocarbon is conventionally known to one of skill in the art, such as, can be the hydrocarbon ils that decompressed wax oil, long residuum, decompressed wax oil blending part reduced pressure residual oil or other secondary processing obtain.The hydrocarbon ils that described other secondary processing obtains as wax tailings, deasphalted oil, furfural treatment raffinate oil in one or more.Mineral oil is selected from one or more the mixture in liquefied coal coil, tar sand oil and shale oil.Synthetic oil is that coal, Sweet natural gas or pitch synthesize the distillate obtained through F-T.Be rich in various animals and plants oils raw materials such as animal grease, the Vegetable oil lipoprotein of hydrocarbon polymer.

The catalyst cracking method of production propylene provided by the invention, make the combined reactor contact reacts that light hydrocarbon and the second catalytic cracking catalyst are being made up of the second riser reactor and fluidized-bed reactor, light hydrocarbon is transformed, reacted oil gas and catalyst separating, regenerate after reacted second catalytic cracking catalyst enters stripper stripping, the catalyzer after regeneration is introduced the second riser reactor and is recycled.Light hydrocarbon and the second catalytic cracking catalyst are introduced the second riser reactor reaction, reacted oil gas and the second catalytic cracking catalyst are not separated the fluidized-bed reactor introduced with the second reactors in series and react; The reacted oil gas of fluidized-bed reactor enters the gas-solid separation equipment of settling vessel then through being connected with settling vessel and enters subsequent product separation system, obtain cracked gas, pyrolysis gasoline, cracking light oil and cracking masout, gas-solid separation equipment is separated the spent agent obtained and enters fluidized bed reaction zone, the reacted oil gas of fluidized-bed reactor and catalyst separating, reacted second catalytic cracking catalyst leaving fluidized bed reaction zone enters the second stripper, returns the second riser reactor and recycle after stripping after introducing in Second reactivator regeneration.The described gas-solid separation equipment be connected with settling vessel such as cyclonic separator.

The catalyst cracking method of production propylene provided by the invention, described light hydrocarbon is gasoline fraction and/or C4 hydrocarbon, comprise gasoline fraction and/or C4 hydrocarbon that product separation system of the present invention obtains, can also containing from the gasoline fraction of other device and/or C4 hydrocarbon; One or more mixture in the gasoline fraction that the optional catalytic cracking raw gasline of other device production gasoline fraction, catalytic cracking stable gasoline, coker gasoline, visbreaker gasoil and other oil refining or chemical process are produced, preferentially selects the gasoline fraction that this device is self-produced.The low-molecular-weight hydrocarbon that described C4 hydrocarbon refers to C 4 fraction to be the normal temperature of main component, exist in gaseous form under normal pressure, comprises alkane, alkene and alkynes that carbonatoms in molecule is 4.It comprises the self-produced gaseous hydrocarbon products being rich in C 4 fraction of this device, also can comprise the hydrocarbon gas being rich in C 4 fraction that other device process is produced, the C 4 fraction that wherein preferably this device is self-produced.Described gasoline fraction is preferably rich in the gasoline fraction of alkene, and described C4 hydrocarbon is preferably rich in the C4 hydrocarbon of alkene.The described content being rich in C4 alkene in the C 4 fraction of alkene is greater than 50 % by weight, is preferably greater than 60 % by weight, preferably more than 70 % by weight; The described olefin(e) centent being rich in the gasoline of alkene is 20 ~ 95 % by weight, preferably 35 ~ 90 % by weight, and preferably more than 50 % by weight.Described gasoline fraction can be the gasoline fraction of full range, and final boiling point is no more than 204 DEG C, and such as boiling range is the gasoline fraction of 30 ~ 204 DEG C or the gasoline fraction of the such as boiling range of narrow fraction wherein between 40 ~ 85 DEG C.Described light hydrocarbon preferably includes gasoline fraction, and in light hydrocarbon, the weight ratio of C4 hydrocarbon and gasoline fraction is 0 ~ 2: 1, and preferably 0 ~ 1.2: 1, most preferably 0 ~ 0.8: 1.The gasoline fraction introducing the second riser reactor is 0.05 ~ 0.20: 1 with the weight ratio of the heavy feed stock injecting the first riser reactor, is preferably 0.08 ~ 0.15: 1.The operational condition of the second riser reactor comprises: when described light hydrocarbon comprises gasoline fraction, it is 10 ~ 30 that gasoline fraction operates agent-oil ratio (introducing the second catalytic cracking catalyst of the second riser reactor and the weight ratio of gasoline fraction) in the second riser tube, and the reaction times is 0.10 ~ 1.5 second; The operation condition of gasoline fraction in second riser reactor: agent-oil ratio is preferably 15 ~ 25, the reaction times is preferably 0.30 ~ 0.8 second, and atomized water steam accounts for gasoline feeding amount preferably 10 ~ 20 % by weight.When described light hydrocarbon comprises C4 hydrocarbon, it is 12 ~ 40 that C4 hydrocarbon operates agent-oil ratio (introducing the second catalytic cracking catalyst of the second riser reactor and the weight ratio of C4 hydrocarbon) in the second riser tube, and the reaction times is 0.50 ~ 2.0 second; The operation condition of C4 hydrocarbon in second riser tube: C4 hydrocarbon is in operation agent-oil ratio (catalyzer and C4 hydrocarbon weight ratio) preferably 17 ~ 30; C4 hydrocarbon is preferably 0.8 ~ 1.5 second reaction times in the second riser tube; The ratio that atomized water steam accounts for C4 inlet amount preferably 15 ~ 25 % by weight.The temperature of reaction of fluidized-bed reactor is 500 ~ 650 DEG C, is preferably 510 ~ 580 DEG C; Weight hourly space velocity is 1 ~ 35 hour ^-1, be preferably 3 ~ 30 hours ^-1; Reaction pressure (absolute pressure) 0.1 ~ 0.4MPa, is preferably 0.15 ~ 0.35MPa.

The catalyst cracking method of production propylene provided by the invention, preferably also the cracking masout that product separation system of the present invention (product separation system) obtains is introduced in the second riser reactor and carry out reacting and/or introduce fluidized-bed reactor and react, to improve low-carbon alkene especially productivity of propylene.When cracking masout introduces the second riser reactor, namely the introducing position of described cracking masout is preferably positioned at the postmedian of the second riser reactor in the part of 1/2nd place's to the second leg outlets of the second riser reactor length (part between riser tube gasoline entrance to outlet), preferably, described cracking masout is introduced in fluidized-bed reactor and is reacted, and more preferably introduces the bottom of described fluidized-bed reactor.The cracking masout produced by this device is incorporated into the second riser reactor postmedian and/or fluidized-bed reactor participates in transforming, the second catalytic cracking catalyst after contacting with light hydrocarbon is utilized to realize the heavy oil conversion degree of depth that heavy oil twice transformation improves whole device on the one hand, utilize cracking masout cut propylene enhancing, the Quench of the gasoline fraction and/or C4 hydrocarbon reaction that are rich in alkene is stopped simultaneously, suppress low-carbon alkene, especially the conversion reaction again after propylene generation, thus be conducive to improving productivity of propylene.Described cracking masout is the cracking masout that product separation system of the present invention obtains, namely most of product liquid that the crackate entering product separation system is remaining after isolating gas, gasoline and diesel oil, its normal pressure boiling range is between 330 ~ 550 DEG C, and preferably its normal pressure boiling range is 350 ~ 530 DEG C.The cracking masout injecting the second riser tube and fluidized-bed reactor is 0.01 ~ 0.30: 1 with the weight ratio of the heavy feed stock injecting the first riser reactor, preferably 0.05 ~ 0.25: 1, its actual cracking masout freshening amount depends on the reaction depth of the first riser tube, and reaction depth larger then cracking masout freshening amount is lower.

The catalyst cracking method of production propylene provided by the invention, reaction oil gas is separated with carbon deposited catalyst by the tripping device of the first riser reactor end, and oil gas product is introduced product separation system and is separated; Successively enter after settling vessel and gas-solid separation equipment isolate the catalyzer wherein carried from the reaction oil gas of the second riser reactor and fluidized-bed reactor, introduce follow-up product separation system.The oil gas product of preferred heavy hydrocarbon oil riser reactor and the oil gas product of fluidized-bed reactor share product separation system, now, are separated introducing separation system after two strands of air-fuel mixtures.In product separation system, oil gas product is isolated to cracked gas, pyrolysis gasoline, cracking light oil and cracking masout.The present invention does not have particular requirement to described product separation system, can refer to prior art.

In the catalyst cracking method of production propylene provided by the invention, described riser reactor be selected from equal diameter riser tube, etc. a kind of in linear speed riser tube and variable diameters riser tube or the wherein combination of two kinds, the first riser reactor wherein transformed for heavy feed stock and identical pattern can be adopted also can to adopt different patterns for the second riser reactor that light hydrocarbon oil transforms.Described fluidized-bed reactor is selected from the combination of one or more in fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed and dense bed reactor.

The catalyst cracking method of production propylene provided by the invention, the operating method of revivifier and operational condition can with reference to Conventional catalytic cracking revivifiers.

The catalyst cracking method of production propylene provided by the invention, heavy feed stock and light hydrocarbon adopt different catalyzer and reaction-regeneration system to transform.The first catalytic cracking catalyst wherein transformed for heavy feed stock with y-type zeolite and β zeolite for chief active constituent element, the catalyzer that should be chief active constituent element with y-type zeolite and β zeolite comprises y-type zeolite and the zeolite beta of at least 10 % by weight by dry basis, contain or do not contain other zeolite, the content of other zeolite is no more than 5 % by weight; With this catalyzer butt weight for benchmark, preferably include (Y+ β) type zeolite of 10 ~ 70 % by weight, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight, more preferably comprise (Y+ β) type zeolite of 25 ~ 50 % by weight, the clay of 25 ~ 50 % by weight, the inorganic oxide binder composition of 25 ~ 50 % by weight.Wherein (Y+ β) type zeolite refers to y-type zeolite and zeolite beta, y-type zeolite in the first described catalytic cracking catalyst: β weight zeolite ratio is 4 ~ 1: 1 ~ 4, and the weight ratio of preferred y-type zeolite and β zeolite is 1.5 ~ 3.5: 3.5 ~ 1.5.Described y-type zeolite is the y-type zeolite generally adopted in prior art, such as, one or more mixture in rare earth Y type zeolite (REY), rare earth hydrogen y-type zeolite (REHY), ultrastable Y－type zeolite (USY) and extremely steady y-type zeolite of rare earth (REUSY).Described zeolite beta is the β zeolite of the various modifications generally adopted in prior art, comprises the β zeolite of phosphorus and transition metal modification.The concrete preparation of zeolite beta can see CN1035668C and CN1041616C.

The catalyst cracking method of production propylene provided by the invention, for the second catalytic cracking catalyst of light hydrocarbon catalytic conversion reaction, be less than 0.7nm with mean pore size and select shape zeolite for chief active constituent element, in described second catalytic cracking catalyst, mean pore size is less than the content that 0.7nm selects shape zeolite and is at least 10 % by weight, contain or do not contain other zeolite, the content of other zeolite is no more than 5 % by weight.Preferably, with catalyzer dry basis, the equal aperture that described second catalytic cracking catalyst comprises 10 ~ 65 % by weight be less than 0.7 nanometer select shape zeolite, 0 ~ 60 % by weight the inorganic oxide binder of clay and 15 ~ 60 % by weight; More preferably by 20 ~ 50 % by weight mean pore size be less than 0.7 nanometer select shape zeolite, 10 ~ 45 % by weight the inorganic oxide binder of clay and 25 ~ 50 % by weight form.The described shape-selective zeolite catalysts being less than 0.7 nanometer containing mean pore size can be the combination of one or more provided by prior art, can be purchased or prepare according to existing method.The shape zeolite of selecting that described mean pore size is less than 0.7 nanometer is selected from ZSM series zeolite, ferrierite, chabazite, dachiardite, erionite, A zeolite, epistilbite, lomontite, and one or more the mixture among the zeolite that obtains after physics and/or chemical process process of above-mentioned zeolite.Described ZSM series zeolite is selected from one or more the mixture in ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38 and ZSM-48 zeolite.The shape zeolite of selecting that preferred mean pore size is less than 0.7 nanometer is one or more in ZSM-5 zeolite, ZRP zeolite, element modified ZRP zeolite or element modified ZSM-5 zeolite, and element modified ZSM-5 zeolite is ZSP zeolite such as.About the more detailed description of ZSM-5 zeolite is see USP3702886, about the more detailed description of ZRP is see USP5232675, CN1211470A, CN1611299A.

Described inorganic oxide binder, can be selected from silicon-dioxide (SiO ₂) and/or aluminium sesquioxide (Al ₂o ₃).Described clay such as kaolin and/or halloysite.

Preferably, for the catalytic cracking unit of the inventive method, at least comprise reactor part, regenerator section and product separation system, reactor adopts double lifting leg and fluidized-bed to form combined reactor configuration, one of them riser tube connect with fluidized-bed reactor after and another riser tube be arranged in juxtaposition mutually, and described riser tube and fluidized-bed reactor cascaded structure further with stripper arranged in series.One dividing plate is set in above-mentioned stripper and is divided into two independent stripping zones, the combined reactor that one of them stripping zone and riser tube and fluidized-bed are formed formed independently react, stripping route, it is for light hydrocarbon oil catalyzed conversion; Another stripping zone then forms to another riser tube that another road corresponding is independently reacted, stripping route, and it is for heavy hydrocarbon oil catalyzed conversion.Wherein can comprise two independently revivifiers, also can arrange a dividing plate to be divided into two independent breeding blankets and to be connected with corresponding independent stripping zone respectively in a revivifier, thus form two strands of relatively independent catalyst reaction, reprocessing cycle routes.Production cyclopropene method of the present invention uses this catalytic cracking unit, can realize adopting different catalyzer to carry out selective conversion to different cuts and distinguishing stripping and regeneration to used catalyst in set of device, simply, effectively two strands of relatively independent catalyst reactions, reprocessing cycle routes are formed, compact construction and easy to implement, device is simple to operate, flexible, the problem using two kinds of different catalysts systems mutually to disturb in same reactor is solved very well engineering, and there is higher productivity of propylene and butylene productive rate, coke and dry gas yied lower.

As shown in Figure 1, described catalytic cracking unit the first stripping zone 51 and the second stripping zone 52 of comprising riser reactor 1, the gas-solid separation equipment 7 be connected with the outlet of riser reactor 1, riser reactor 2 and the fluidized-bed reactor 3 of connecting with it, the gas-solid separation equipment 8 of fluidized-bed reactor, settling vessel 9, stripper dividing plate 5 and being separated by dividing plate 5; The catalyst outlet of gas-solid separation equipment 7 is communicated with the first stripping zone 51, and the top of the first stripping zone 51 is communicated with settling vessel 9; The catalyst outlet of gas-solid separation equipment 8 is communicated with the second stripping zone 52 or fluidized-bed reactor 3 is communicated with, the entrance of gas-solid separation equipment 8 is communicated with settling vessel 9, the top of fluidized-bed reactor 3 is communicated with settling vessel 9, the bottom of fluidized-bed reactor 3 is communicated with stripper 52, is communicated with after gas-solid separation equipment 7 is connected with the oil gas vent of gas-solid separation equipment 8 with oil and gas separating system.Described revivifier can be two independent revivifiers, also can be as shown in Figure 1 a revivifier is divided into two breeding blankets, the dividing plate 6 wherein settled in revivifier 4, is divided into two breeding blankets 61 and 62, is connected respectively with stripping zone 51 with 52 by revivifier 4.In order to freshening cracking masout, described riser reactor 2 and/or fluidized-bed reactor 3 also comprise cracking masout entrance.Riser reactor 2 can be connected with fluidized-bed through stripper, also can be arranged at stripper outer (external riser tube).Fluidized-bed combined reactor 3 is connected with stripping zone 52, stripping steam can be realized and introduce fluidized-bed reactor, reactor is discharged after making it pass fluidized-bed reactor, both oil gas dividing potential drop can effectively be reduced, shorten oil gas in the settling section residence time, be conducive to propylene enhancing, reduce dry gas, coke yield.Described dividing plate 5 preferably also extends in settling vessel, the bottom of settling vessel is divided into two regions do not communicated, be used separately as the settling vessel of combined reactor that riser reactor 2 and fluidized-bed reactor 3 form and riser reactor 1, preferably two negative areas are communicated with at the top of settling vessel 5, the headspace of public settling vessel 9.

In the combined reactor that described riser reactor 2 and fluidized-bed reactor 3 form, leg outlet is preferably also containing low tension outlet sparger, and the pressure drop of this low tension outlet sparger is less than 10KPa.

Be further described below in conjunction with accompanying drawing 1 pair of the inventive method:

First catalytic cracking catalyst of being derived by the first breeding blanket 61 of revivifier 4 enters bottom riser reactor 1 through regenerator inclined tube 40, second catalytic cracking catalyst of being derived by breeding blanket 62 enters bottom riser reactor 2 through regenerator inclined tube 41, and correspondingly two strands of catalyzer accelerate upwards to flow respectively under the pre-lift medium effect of being injected by pipeline 22 and 23.Heavy feed stock after preheating (heavy hydrocarbon or be rich in the various animals and plants oils of hydrocarbon polymer) is after pipeline 20 mixes by a certain percentage with the atomizing steam from pipeline 21, injecting lift pipe reactor 1, oil gas carbon deposited catalyst after reaction is separated with the fast separating device 7 of catalyst mixture through riser tube 1 end by reaction oil gas; The light hydrocarbon (being such as rich in gasoline fraction and/or the C4 hydrocarbon of alkene) of preheating simultaneously or not preheating is after pipeline 24 mixes by a certain percentage with the atomizing steam from pipeline 25, injecting lift pipe reactor 2, thereafter reaction oil gas and catalyst mixture are along in riser tube 2 upwards flowing-path, reaction oil gas and catalyst mixture continue reaction after the outlet distributor (not marking in figure) of riser tube 2 enters fluidized-bed reactor 3, carry out being separated of oil gas and catalyzer after finally entering settling vessel 9 through gas-solid separation equipment 8.All hydrocarbon oil product, comprise the oil gas of riser tube 1 outlet and all collected by settling vessel top cyclone separation system (not marking figure) from the oil gas that fluidized-bed reactor 3 flows out, drawing reactor by pipeline 26 and enter subsequent product separation system (not marking in figure).In product separation system, catalytic pyrolysis product separation is hydrocarbon gas, pyrolysis gasoline, cracking light oil, cracking masout and cracking slurry oil.Cracked gaseous hydrocarbons is separated at subsequent product, refining after can obtain polymerization-grade propylene product and be rich in the C 4 fraction of alkene, the C 4 fraction being wherein rich in alkene can transform production propylene by Returning reactor again, preferably the C 4 fraction being rich in alkene is returned riser reactor 2 or fluidized-bed reactor 3 transforms again.Pyrolysis gasoline can partly or entirely transform by Returning reacting system again; Also can first gasoline be cut into gently, heavy naphtha section, the part or all of Returning reacting system of petroleum naphtha transforms again, preferably petroleum naphtha is returned the second reactor and transforms.

The first catalytic cracking catalyst through the isolated carbon deposit of fast separating device 7 of riser reactor 1 end introduces stripping zone 51, the second catalytic cracking catalyst obtained after separating device 8 is separated enters fluidized-bed reactor 3, mix with the oil agent mixture being entered fluidized-bed reactor 3 by riser reactor 2, then enter stripping zone 52; Stripped vapor injects through pipeline 50, and with carbon deposited catalyst counter current contact, by the reaction oil gas entrained by carbon deposited catalyst, stripping is clean as much as possible, finally enters settling vessel 9, draws reactor together with other oil gas after gas-solid separation equipment 8 is separated by pipeline 26.Stripping zone 51 after stripping and the catalyzer of stripping zone 52 send into two independent breeding blankets 61 respectively by spent agent inclined tube 42 and 43 and coke burning regeneration is carried out in breeding blanket 62.Oxygen-containing gas such as air injects revivifier 4 through pipeline 60, and the regenerated flue gas that two regeneration is gone is drawn through pipeline 63 through the top public space mixing at revivifier 4.Catalyzer after regeneration returns riser reactor 1 and 2 respectively through regenerator inclined tube 40 and 41 and recycles.

In above-mentioned embodiment process, introduce pre-lift medium by pipeline 22 and 23 respectively to riser tube 1 and riser tube 2.Described pre-lift medium is known for those skilled in the art, can be selected from one or more in water vapor, C1 ~ C4 hydro carbons or Conventional catalytic cracking dry gas, preferably water steam and/or be rich in the C 4 fraction of alkene.

The following examples will be further described the present invention.

The raw material used in embodiment and comparative example comprises raw material A, raw material B, raw material C and raw material D, wherein raw material A and B are two kinds of different heavy oil fractions, raw material C and raw material D is respectively the pyrolysis gasoline and routine full cut catalytic cracking product gasoline that are rich in alkene, and specific nature is in table 1.The catalyzer adopted is respectively CHP and MMC-2 and two kind of the laboratory that Sinopec catalyzer asphalt in Shenli Refinery produces and prepares the catalyzer that name is called Y and BY, its specific nature is in table 2, wherein its chief active constituent element of Y catalyzer is y-type zeolite (USY), its chief active constituent element of BY catalyzer is y-type zeolite (USY) and β zeolite, its chief active constituent element of CHP catalyzer is ZRP zeolite, and its active component of MMC-2 catalyzer is y-type zeolite (USY) and ZRP zeolite.In above-mentioned four kinds of catalyzer, to account for the ratio of catalyzer total amount substantially suitable for active component.Four kinds of catalyzer all carry out 790 DEG C × 100%H ₂the steam aging pre-treatment of O × 14 hour (namely in 790 DEG C, under 100% water vapour atmosphere aging 14 hours).

Laboratory catalytic agent Y and BY is prepared according to existing method, its preparation process is as follows: water, kaolin, pseudo-boehmite and hydrochloric acid are added plastic cans by (1) successively, stir, wherein the consumption of water makes the solid content of the slurries obtained be 30 % by weight, and hydrochloric acid (in HCl) is 0.18: 1 with the mol ratio of pseudo-boehmite (in aluminum oxide); (2) gained slurries are warming up to 65 DEG C, stop stirring, static aging 1h; (3) be cooled to 50 DEG C, add Alumina gel and zeolite slurry (content of zeolite slurry mesolite is 30 % by weight) successively, stir; (4) slurries are spray-dried shaping, washing, the obtained catalyst sample of oven dry.Wherein, Y catalyzer contains USY zeolite 35 % by weight, kaolin 35 % by weight, pseudo-boehmite (in aluminum oxide) 26 % by weight, Alumina gel (in aluminum oxide) 4 % by weight.BY catalyzer is containing USY zeolite and β zeolite 35 % by weight, kaolin 35 % by weight, pseudo-boehmite (in aluminum oxide) 26 % by weight, Alumina gel (in aluminum oxide) 4 % by weight, wherein y-type zeolite: zeolite beta=2: 3 (mass ratioes).The zeolite of USY described in catalyzer content of rare earth 2 % by weight, silica alumina ratio (SiO ₂/ Al ₂o ₃mol ratio) 5.2; Silica alumina ratio (the SiO of β zeolite ₂/ Al ₂o ₃mol ratio) be 30, be Hydrogen β zeolite, be catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product.

Comparative example 1

Experiment is carried out in small fixed flowing bed (FFB) catalytic cracking unit.This apparatus design is interval type, single-pass operation pattern.Raw material is heavy oil A, and catalyzer is BY.

Heavy oil A as shown in table 2 enters in fluidized-bed reactor and carries out catalyzed reaction with BY catalyst exposure, and reaction conditions is: temperature of reaction is 520 DEG C, agent-oil ratio 6, weight hourly space velocity 15h ^-1, water filling quantity of steam is 5 % by weight.Reaction product, steam are separated in settling vessel with spent agent, and reaction product isolated obtains gaseous product and product liquid, and spent agent catalyzer is gone out the hydrocarbon product that spent agent adsorbs by water vapor stripping.Spent agent after stripping and heated hot air regenerate, and the catalyzer after regeneration carries out new catalytic conversion reaction again.Test conditions and main result are in table 3.

Comparative example 2

FFB device described in comparative example 1 is tested.Raw material is identical with comparative example 1 with reaction conditions, is Y unlike catalyzer, the prevailing operating conditions of experiment and the results are shown in table 3.。

Comparative example 3

Experiment is carried out in small fixed flowing bed (FFB) catalytic cracking unit.Raw material is heavy oil B, and catalyzer is CHP.

Heavy oil B as shown in table 2 enters in fluidized-bed reactor and carries out catalyzed reaction with CHP catalyst exposure, and reaction conditions is: temperature of reaction is 580 DEG C, agent-oil ratio 5, weight hourly space velocity 1h ^-1, water filling quantity of steam is 30 % by weight.Reaction product, steam are separated in settling vessel with spent agent, and reaction product isolated obtains gaseous product and product liquid, and spent agent catalyzer is gone out the hydrocarbon product that spent agent adsorbs by water vapor stripping.Spent agent after stripping and heated hot air regenerate, and the catalyzer after regeneration carries out new catalytic conversion reaction again.Test conditions and main result are in table 3.

Comparative example 4

FFB device described in comparative example 3 is tested.Catalyzer is identical with comparative example 3 with reaction conditions, becomes raw material D unlike stock oil.Experiment prevailing operating conditions and the results are shown in table 3.

Comparative example 5

FFB device described in comparative example 4 is tested.Reaction conditions is identical with comparative example 4 with comparative example 3 with catalyzer, is not both raw material and changes, the prevailing operating conditions of experiment and the results are shown in table 3.

Embodiment 1

Experiment is carried out at kitty cracker.This device comprises two and overlaps independently reaction-regeneration system: the first riser reactor, and internal diameter is 16 millimeters, and length is 3800 millimeters, and catalyzer used is BY catalyzer, and the raw material A shown in his-and-hers watches 1 carries out cracking; Oil gas after conversion and catalyst separating, catalyzer enters the first revivifier regeneration after entering the first stripper, the catalyzer after regeneration returns the first riser reactor and recycles; Oil gas is introduced product separation system and is separated.In second riser reactor, warp is 16mm, length is 3200mm, series fluidized bed reactor after second riser reactor, the diameter of fluidized-bed reactor is 64 millimeters for (internal diameter), height 600 millimeters, gasoline fraction (boiling range is 30 ~ 85 DEG C) from product separation system is transformed, catalyzer used is CHP, oil gas after conversion and catalyst separating, catalyzer enters Second reactivator regeneration after entering the second stripper, the catalyzer after regeneration returns the second riser reactor and recycles; Oil gas is introduced product separation system and is separated.The oil gas obtained after first riser reactor reaction is separated in identical product separation system with after the air-fuel mixture obtained after fluidized-bed reactor reaction.Oil gas after second stripper stripping enters corresponding settling vessel through fluidized-bed reactor.Its reaction and operational condition and reaction result are in table 4.

Comparative example 6

Experiment is carried out at kitty cracker, and riser tube adds fluidized-bed reaction.

In riser reactor, warp is 16mm, be highly 3200mm, series fluidized bed reactor after riser reactor, the diameter of fluidized-bed reactor is 64 millimeters for (internal diameter), height 600 millimeters, raw material A shown in his-and-hers watches 1 transforms, and catalyzer used is MMC-2 (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, containing y-type zeolite and ZRP zeolite).Oil gas after conversion and catalyst separating, catalyzer enters revivifier regeneration after entering stripper, the catalyzer after regeneration returns riser reactor and recycles; Oil gas product is introduced product separation system and is separated.Oil gas after stripper stripping enters corresponding settling vessel through fluidized-bed reactor.Its reaction and operational condition and reaction result are in table 4.

Embodiment 2

With reference to embodiment 1, in the second riser reactor, introduce unlike exporting 1.5 meters of at distance the second riser reactor the cracking masout (boiling range of cracking masout is 350 ~ 500 DEG C) that product separation system obtains, the introduction volume of described cracking masout and the weight ratio of raw material A are 0.05: 1.

Embodiment 3

According to the method for embodiment 2, introduce bottom fluidized-bed reactor unlike cracking masout, and in the second riser reactor, do not introduce described cracking masout.

Embodiment 4

Use reaction unit provided by the invention.As shown in Figure 1, this middle-scale device riser reactor 1 internal diameter is 16 millimeters, and length is 3800 millimeters; The internal diameter of riser reactor 2 is 16 millimeters, and length is 3200 millimeters, and adopts external riser tube pattern to arrange.Riser reactor 2 exports and connects fluidized-bed reactor 3, and the cross section semicircular in shape of this fluidized-bed reactor, it is 64 millimeters of circular area that its cross-sectional area equals diameter, length 600 millimeters.Settling vessel 9 length is 1520mm, diameter is 250mm, wherein stripper dividing plate 5 is straight plate, stripper is divided into two portions, the sectional area forming the stripping zone 51 of circulating with riser reactor 1 accounts for 85% of whole stripping stage sectional area, and stripper dividing plate 5 extends to settling vessel, along distance settling vessel top 500mm on dividing plate.Test adopts freshening mode to operate.Be that BY introduces the first riser reactor and reacts by raw material B and catalyzer, reacted oil gas enters fast separating device and is separated, catalyzer after separation enters stripping zone 51, introduce breeding blanket 61 after stripping to regenerate, oil gas with enter product separation system after the air-fuel mixture of fluidized-bed reactor and be separated, being separated the light gasoline fraction (boiling range is 30 ~ 85 DEG C) obtained introduces bottom riser reactor 2, its amount is 0.15: 1 with the weight ratio of raw material B, react with the CHP catalyst exposure introducing riser reactor 2, then enter fluidized-bed reactor 3 to react, oil gas after fluidized-bed reaction enter settling vessel isolated the catalyzer wherein carried by gas-solid separator 8 after with the air-fuel mixture of riser reactor 1 after enter product separation system, catalyzer in fluidized-bed reactor enters stripping zone 52 from leaving bottom it, enter breeding blanket 62 after stripping to regenerate, oil gas after stripper 52 stripping enters settling vessel through fluidized-bed reactor 3.Its operational condition and reaction result are in table 4.

From table 4, compared with the conventional method, the method for production propylene provided by the invention, can improve heavy oil conversion performance, reduces dry gas and coke yield while the gain in yield of propylene and butylene.Further by by bottom cracking masout freshening to the second riser reactor postmedian or fluidized-bed reactor, heavy oil yield can be reduced further, increase the productive rate of propylene and iso-butylene.The net-structure apparatus that the present invention proposes transforms, and can reduce heavy oil yield, increases the productive rate of propylene and iso-butylene, improve the yield of high-value product, and apparatus structure is compact.

Table 1

Title	Raw material A	Raw material B	Raw material C	Raw material D
					Density/(g/cm ³)	0.8617	0.8808	0.6696	0.7246
Refractive index (n _d ⁷⁰)	1.461	1.4741	/	/
					Kinematic viscosity/(mm ²/s)100℃	4.864	5.23	/	/
Condensation point/DEG C	42	44	/	/
					W (carbon residue)/%	0.02	0.24	/	/
Elementary composition
					C/H/ % by weight	86.30/13.63	85.46/12.75	85.18/14.44	86.29/13.54
S/N/ % by weight	0.06/0.08	0.33/0.14	0.015/0.001	0.055/0.007
					Boiling range/DEG C
Initial boiling point	286	256	32	38
					5％	343	303	39	47
10％	368	328	40	51
					30％	410	374	44	62
50％	37	405	48	80
					70％	465	440	53	112
90％	498	499	65	155
					95％	512	535	69	170
Final boiling point	/	/	77	192
					Group composition, % by weight
Alkane	/	/	22.19	22.79
					Alkene	/	/	72.60	57.81
Naphthenic hydrocarbon	/	/	3.45	6.60
					Aromatic hydrocarbons	/	/	1.76	12.80

Table 2

Catalyzer title	Y	BY	CHP	MMC-2
					Chief active constituent element	USY	USY+β	ZRP	USY+ZRP
Chemical property, % by weight
					Al ₂O ₃	53.1	50.6	51	52.3
Na ₂O	/	/	0.066	0.072
					RE ₂O ₃	0.67	/	/	/
Physical properties
					Total pore volume, ml/g	0.196	0.165	0.22	0.164
Specific surface, m ²/g	144	129	105	113
					Micro-activity, w%	69	66	52	64

Table 3

Case	Comparative example 2	Comparative example 1	Comparative example 3	Comparative example 4	Comparative example 5
						Stock oil	Raw material A	Raw material A	Raw material B	Raw material D	Raw material C
Catalyzer	Y	BY	CHP	CHP	CHP
						Temperature of reaction, DEG C	520	520	580	580	580
Agent-oil ratio	6	6	5	5	5
						Air speed, 1/h	15	15	1	1	1
Water filling quantity of steam, % by weight	5	5	30	30	30
						Material balance, % by weight
Dry gas	5.85	3.27	9.03	5.31	9.78
						Liquefied gas	30.71	31.58	34.39	32.76	46.52
C5 gasoline (C5 ~ 221 DEG C, TBP)	45.46	43.28	30.27	55.47	39.08
						Diesel oil (221 ~ 330 DEG C, TBP)	8.01	9.85	11.76	2.74	1.54
Heavy oil (> 330 DEG C, TBP)	4.24	5.74	7.83	1.74	0.19
						Coke	5.73	6.28	6.72	1.98	2.89
Amount to	100.00	100.00	100.00	100.00	100.00
						Transformation efficiency/%	87.75	84.41
Small-numerator olefin productive rate, % by weight
						Hydrogen yield	/	/	0.55	0.08	0.12
Ethylene yield	/	/	3.70	4.04	7.95
						Productivity of propylene	/	/	16.87	21.90	24.41
Butylene productive rate	/	/	10.55	8.80	14.43
						Ethene+propylene+butylene	/	/	31.12	34.74	46.78
Product selectivity
						Gasoline, %	51.81	51.27	/	/	/
Product gasoline forms
						Alkene, % by weight	16.62	28.29	/	/	/

Table 4

Claims

1. produce a catalyst cracking method for propylene, comprising:

(1) heavy feed stock and the first catalytic cracking catalyst contact reacts in the first riser reactor being chief active constituent element with y-type zeolite and zeolite beta is made, reacted oil gas is separated with the first catalytic cracking catalyst, oil gas introduces product separation system, first catalytic cracking catalyst introduces the first revivifier regeneration after the first stripper stripping, and regenerated catalyst is introduced the first riser reactor and recycled; First riser reactor temperature of reaction is 450 ~ 650 DEG C, and agent-oil ratio is 1 ~ 25, and the reaction times is 0.50 ~ 10 second;

(2) make light hydrocarbon and be less than 0.7nm with aperture and select the second catalytic cracking catalyst that shape zeolite is chief active constituent element in the second riser reactor contact reacts, reacted oil gas and reacted second catalytic cracking catalyst are introduced the fluidized-bed reactor of connecting with the second riser reactor and are reacted; The reacted oil gas of fluidized-bed reactor introduces product separation system, reacted second catalytic cracking catalyst introduces Second reactivator regeneration after introducing the second stripper stripping, the second catalytic cracking catalyst after regeneration is introduced the second riser reactor and recycled; Described light hydrocarbon comprises gasoline fraction and/or C4 hydrocarbon; When comprising gasoline fraction, the agent-oil ratio that gasoline fraction operates in the second riser reactor is 10 ~ 30, and the reaction times is 0.10 ~ 1.5 second; When described light hydrocarbon comprises C4 hydrocarbon, it is 12 ~ 40 that C4 hydrocarbon operates agent-oil ratio in the second riser tube, and the reaction times is 0.50 ~ 2.0 second; The temperature of reaction of fluidized-bed reactor is 500 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 35 hour ^-1.

2. in accordance with the method for claim 1, it is characterized in that, with catalyzer butt weight for benchmark, the first described catalytic cracking catalyst comprises 10 ~ 70 % by weight zeolites, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight, y-type zeolite in described zeolite: weight ratio=4 ~ 1 of zeolite beta: 1 ~ 4.

3. in accordance with the method for claim 2, it is characterized in that, described first catalytic cracking catalyst comprises Y and zeolite beta, the clay of 25 ~ 50 % by weight, the inorganic oxide binder of 25 ~ 50 % by weight of 25 ~ 50 % by weight.

4. in accordance with the method for claim 1, it is characterized in that, with the second catalytic cracking catalyst dry basis, the second described catalytic cracking catalyst comprises zeolite, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight of 10 ~ 65 % by weight, and described zeolite is that aperture is less than 0.7nm and selects shape zeolite.

5. in accordance with the method for claim 1, it is characterized in that, the aperture that the second described catalytic cracking catalyst comprises 20 ~ 50 % by weight is less than 0.7nm and selects shape zeolite, the clay of 10 ~ 45 % by weight, the inorganic oxide binder of 25 ~ 50 % by weight.

6. according to catalyst cracking method according to claim 1, it is characterized in that, the temperature of reaction of the first riser reactor is 480 ~ 600 DEG C, and agent-oil ratio is 5 ~ 20, and the reaction times is 1 ~ 10 second.

7. according to catalyst cracking method according to claim 1, it is characterized in that, described heavy feed stock is heavy hydrocarbon or the various animals and plants oils raw materials being rich in hydrocarbon polymer, and described heavy hydrocarbon is selected from one or more the mixture in petroleum hydrocarbon, mineral oil and synthetic oil.

8. according to the catalyst cracking method described in any one of claim 1 ~ 7, it is characterized in that, described light hydrocarbon comprises gasoline fraction from described product separation system and/or C4 hydrocarbon.

9. according to the method described in any one of claim 1 ~ 7, it is characterized in that, also the cracking masout that described product separation system obtains is introduced the postmedian of the second riser reactor and/or the bottom of fluidized-bed reactor.

10. according to catalyst cracking method according to claim 1, it is characterized in that, catalytic cracking unit used comprises: the gas-solid separation equipment (8) of riser reactor (1), the gas-solid separation equipment (7) be connected with the outlet of riser reactor (1), riser reactor (2) and the fluidized-bed reactor (3) of connecting with riser reactor (2), fluidized-bed reactor, settling vessel (9), stripper dividing plate (5) and the first stripping zone (51) separated by dividing plate (5) and the second stripping zone (52); The top of the first stripping zone (51) is communicated with settling vessel (9); The entrance of gas-solid separation equipment (8) is communicated with settling vessel (9), is communicated with after gas-solid separation equipment (7) is connected with the oil gas vent of gas-solid separation equipment (8) with oil and gas separating system; The top of fluidized-bed reactor (3) is communicated with settling vessel (9), and the bottom of fluidized-bed reactor (3) is communicated with the second stripping zone (52).

11. in accordance with the method for claim 10, it is characterized in that, also comprise revivifier (4), one dividing plate (6) is set in revivifier (4) and is divided into two independent breeding blankets (61) and (62), be connected with (52) with stripping zone (51) respectively.

12., according to the method described in claim 10 or 11, is characterized in that, described riser reactor (2) and/or fluidized-bed reactor (3) also comprise cracking masout entrance.